Transition metal complex, catalyst composition including the same and olefin polymer using catalyst composition

ABSTRACT

Provided are a novel transition metal complex where a monocyclopentadienyl ligand to which an amido group is introduced is coordinated, a catalyst composition including the same, and an olefin polymer using the catalyst composition. The transition metal complex has a pentagon ring structure having an amido group connected by a phenylene bridge in which a stable bond is formed in the vicinity of a metal site, and thus, a sterically hindered monomer can easily approach the transition metal complex. By using a catalyst composition including the transition metal complex, a linear low density polyolefin copolymer having a high molecular weight and a very low density polyolefin copolymer having a density of 0.910 g/cc or less can be produced in a polymerization of monomers having large steric hindrance. Further, the reactivity for the olefin monomer having large steric hindrance is excellent.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This application is a divisional application of U.S. application Ser.No. 11/689,917, filed on Mar. 22, 2007, which claims priority to KoreanPatent Application No. 10-2006-0026992, filed on Mar. 24, 2006, and allthe benefits accruing therefrom under 35 U.S.C. §119, the contents ofwhich in its entirety are herein incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel transition metal complex wherea monocyclopentadienyl ligand to which an amido group is introduced iscoordinated, a catalyst composition including the same, and an olefinpolymer using the catalyst composition, and more particularly, to anovel transition metal complex containing a phenylene bridge, a catalystcomposition including the same, and an olefin polymer using the catalystcomposition.

2. Description of the Related Art

In the early 1990s, Dow Chemical Co. developed Me₂Si(Me₄C₅)(NtBu)TiCl₂(Constrained-Geometry Catalyst, hereinafter referred to as CGC) (U.S.Pat. No. 5,064,802). CGC shows excellent properties in acopolymerization reaction of ethylene and α-olefin, compared toconventional metallocene catalysts. For example, (1) CGC can be used toform high molecular weight polymers due to its high reactivity at highpolymerization temperature, and (2) CGC can be used for copolymerizationof α-olefin having large steric hindrance, such as 1-hexene and1-octene. Due to many useful properties, in addition to these propertiesdescribed above, obtained from use of CGC, research into synthesis ofCGC derivatives as a polymerization catalyst is substantially increasingin academic and industrial fields.

For example, synthesis of metal complexes comprising other variousbridges instead of a silicon bridge and containing a nitrogensubstituent, and polymerization using these metal complexes wereperformed. Examples of such metal compounds include Complexes 1 through4 (Chem. Rev. 2003, 103, 283).

Complexes 1 through 4 respectively contain a phosphorus bridge, anethylene or propylene bridge, a methyllidene bridge, and a methylenebridge, instead of the silicon bridge of the CGC structure. However,these complexes show low activity or poor copolymerization performancewhen ethylene is polymerized or when ethylene and α-olefin arecopolymerized, compared to CGC.

In addition, the amino ligand in CGC can be replaced with an oxidoligand. Some of such complexes were used for polymerization. Examples ofsuch complexes include the following Formulae.

In Complex 5, which was developed by T. J. Marks et al., acyclopentadiene (Cp) derivative is bridged to an oxido ligand byortho-phenylene group (Organometallics 1997, 16, 5958). A complex havingthe same bridge and polymerization using the complex were suggested byMu et al. (Organometallics 2004, 23, 540). A complex in which an indenylligand is bridged to an oxido ligand by an ortho-phenylene group wasdeveloped by Rothwell et al. (Chem. Commun. 2003, 1034). In Complex 6,which was developed by Whitby et al., a cyclopentadienyl ligand isbridged to an oxido ligand by three carbon atoms (Organometallics 1999,18, 348). It was reported that Complex 6 showed reactivity insyndiotactic polystylene polymerization. Similar complexes to Complex 6were developed by Hessen et al. (Organometallics 1998, 17, 1652).Complex 7, which was developed by Rau et al., showed reactivity whenbeing used for ethylene polymerization and ethylene/1-hexenecopolymerization at high temperature and high pressure (210□, 150 Mpa)(J. Organomet. Chem. 2000, 608, 71). Complex 8, which has a similarstructure to Complex 7 and was developed by Sumitomo Co. (U.S. Pat. No.6,548,686), can be used for high temperature and high pressurepolymerization.

However, only some of these catalysts described above are usedcommercially. Accordingly, there is still a need to develop a catalystinducing high polymerization performance.

SUMMARY OF THE INVENTION

The present invention provides a novel transition metal complex having aphenylene bridge.

The present invention also provides a novel organic amine-basedcompound.

The present invention also provides a catalyst composition including thetransition metal complex.

The present invention also provides a method of preparing the catalystcomposition.

The present invention also provides a method of preparing an olefinpolymer using the catalyst composition.

The present invention also provides an olefin polymer prepared using themethod.

According to an aspect of the present invention, there is provided atransition metal complex represented by Formula 1 below.

Here, R₁s and R₂s are each independently a hydrogen atom; a C₁₋₂₀ alkyl,C₆₋₂₀ aryl or silyl radical; a C₂₋₂₀ alkenyl, C₇₋₂₀ alkylaryl, or C₇₋₂₀arylalkyl ra metalloid radical of Group 14 substituted with a C₁₋₂₀hydrocarbyl, wherein R₁ and R₂ can be connected to each other by analkylidine radical containing a C₁₋₂₀ alkyl or aryl radical to form aring;

each of the R_(a)s are independently a hydrogen atom; or a halogenradical; or a C₁₋₂₀ alkyl, C₆₋₂₀ aryl, C₁₋₂₀ alkoxy, C₆₋₂₀ aryloxy, oramido radical, wherein at least two R₃′s can be connected to each otherto form an aliphatic or aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring;

M is a Group 4 transition metal; and

Q₁ and Q₂ are each independently a halogen radical; a C₁₋₂₀ alkylamido,or C₆₋₂₀ arylamido radical; a C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₆₋₂₀ aryl,C₇₋₂₀ arylalkyl radical; or a C₁₋₂₀ alkylidene radical.

The transition metal complex represented by Formula 1 may be representedby Formula 2 below.

Here, R₄s and R₅s are each independently a hydrogen atom; or a C₁₋₂₀alkyl, C₆₋₂₀ aryl or silyl radical;

each of the R₆s are each independently a hydrogen atom; or a C₁₋₂₀ alkylor C₆₋₂₀ aryl radical; a C₂₋₂₀ alkenyl, C₇₋₂₀ alkylaryl or C₇₋₂₀arylalkyl radical; or a C₁₋₂₀ alkoxyl, C₆₋₂₀ aryloxyl or amido radical,wherein at least two R₆'s can be connected to each other to form analiphatic or aromatic ring;

Q₃ and Q₄ are each independently a halogen radical; a C₁₋₂₀ alkylamidoor C₆₋₂₀ arylamido radical; or a C₁₋₂₀ alkyl radical; n is a integersuch as 0 or 1; and

M is a Group 4 transition metal.

The transition metal complex represented by Formula 1 may be representedby one of the following Formulae.

Here, each of the R₇s are independently a hydrogen atom or a methylradical, and

Q₅ and Q₆ are each independently a methyl, dimethylamido or chlorideradical.

According to another aspect of the present invention, there is providedan amine-based compound represented by Formulae 3 and 4 below.

Here, R₁, R₂ and R₃ are described above. And n is a integer such as 0 or1.

According to another aspect of the present invention, there is provideda catalyst composition including: a transition metal complex representedby Formula 1; and at least one cocatalyst compound selected from thegroup consisting of compounds represented by Formulae 5, 6, and 7 below.

Here, CY1, R₁, R₂, R₃, Q₁ and Q₂ are described above.

—[Al(R₈)—O]_(a)—  Formula 5

Here, each of the R₈s are independently a halogen radical; a C₁₋₂₀hydrocarbyl radical; and a C₁₋₂₀ hydrocarbyl radical substituted with ahalogen atom, or a is an integer of 2 or greater.

D(R₈)₃   Formula 6

Here, D is aluminum or boron, and R₈ is described above.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  Formula 7

Here, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z isa Group 13 atom; and each of the As are independently a C₆₋₂₀ aryl orC₁₋₂₀ alkyl radical in which at least one hydrogen atom is substitutedwith a halogen atom, or a C₁₋₂₀ hydrocarbyl, C₁₋₂₀ alkoxy, or phenoxyradical.

The transition metal complex represented by Formula 1 of the catalystcomposition may be one of compounds represented by the followingFormulae.

Here, R₇, Q₅ and Q₆ are described above.

According to another aspect of the present invention, there is provideda method of preparing a catalyst composition including: bringing thetransition metal complex represented by Formula 1 below into contactwith a compound represented by Formula 5 or 6 below to obtain a mixture;and adding a compound represented by Formula 7 below to the mixture.

Here, CY1, R₁, R₂, R₃, R₈, Q₁, Q₂, a, D, L, H, Z and A are describedabove.

The transition metal complex represented by Formula 1 in the method ofpreparing the catalyst composition may be one of compounds representedby the following Formulae.

Here, R₇, Q₅ and Q₆ are described above.

The molar ratio of the transition metal complex to the compoundrepresented by Formula 5 or 6 may be in the range of 1:2 to 1:5000, andthe molar ratio of the transition metal complex to the compoundrepresented by Formula 7 may be in the range of 1:1 to 1:25.

According to another aspect of the present invention, there is provideda method of synthesizing an olefin polymer, wherein the catalystcomposition is brought into contact with a monomer.

The monomer may be at least one monomer selected from the groupconsisting of ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.

According to another aspect of the present invention, there is providedan olefin polymer synthesized using the method of synthesizing an olefinpolymer.

The monomer that is used to synthesize the olefin polymer may include:ethylene; and at least one comonomer selected from the group consistingof propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

A transition metal complex according to an embodiment of the presentinvention has an amido group connected by a phenylene bridge, so that asterically hindered monomer easily approaches the transition metalcomplex and a pentagon ring structure of the transition metal complex isstably maintained, compared to a conventional transition metal complexhaving a silicon bridge and an oxido ligand. By using a catalystcomposition including the transition metal complex according to anembodiment of the present invention, a polyolefin copolymer having avery low density less than 0.910 g/cc can be obtained.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the present invention will be described in detail byexplaining embodiments of the invention The invention may, however, beembodied in many different forms and should not be construed as beinglimited to the embodiments set forth herein; rather, these embodimentsare provided so that this disclosure will be thorough and complete, andwill fully convey the concept of the invention to those skilled in theart.

A transition metal complex according to an embodiment of the presentinvention may be represented by Formula 1 below.

Here, R₁s and R₂s are each independently a hydrogen atom; a C₁₋₂₀ alkyl,C₆₋₂₀ aryl or silyl radical; a C₂₋₂₀ alkenyl, C₇₋₂₀ alkylaryl, or C₇₋₂₀arylalkyl radical; or a metalloid radical of Group 14 substituted with aC₁₋₂₀ hydrocarbyl, wherein R₁ and R₂ can be connected to each other byan alkylidine radical containing a C₁₋₂₀ alkyl or aryl radical to form aring;

each of the R₃s are independently a hydrogen atom; a halogen radical; ora C₁₋₂₀ alkyl, C₆₋₂₀ aryl, C₁₋₂₀ alkoxy, C₆₋₂₀ aryloxy, or amidoradical, wherein at least two R₃s can be connected to each other to forman aliphatic or aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring;

M is a Group 4 transition metal; and

Q₁ and Q₂ are each independently a halogen radical; a C₁₋₂₀ alkylamido,or

C6-20 arylamido radical; a C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₆₋₂₀ aryl, C₇₋₂₀arylalkyl radical; and a C₁₋₂₀ alkylidene radical.

A metal site of the transition metal complex represented by Formula 1according to the current embodiment of the present invention isconnected to a cyclopentadienyl ligand which is connected to a phenylenebridge to which a ring shaped amido group is introduced. Thus, by itsstructural inherence the angle of Cp-M-N structure tends to be narrow,and a wide angle tends to be maintained in the Q₁-M-Q₂ structure towhich a monomer approaches. In addition, compared to a CGC structurethat includes a silicon bridge, the transition metal complex representedby Formula 1 has a stable and strong ring in which Cp, a phenylenebridge, nitrogen, and a metal site forms a pentagon structure. That is,a securer complex compound structure can be obtained since the nitrogenatom in the amido group is cyclically connected to the phenylene bridgethrough two bonds. Accordingly, when the complex compound which isactivated by a cocatalyst such as methylaluminoxane or B(C₆F₅)₃, isapplied to the synthesis of polyolefin, a polyolefin which has a highactivity, a high molecular weight, and a high degree of copolymerizationcan be obtained even at a high reaction temperature. In particular, avery low density polyolefin copolymer having a density of 0.910 g/cc orless as well as 0.910˜0.930 g/cc can also be prepared since thestructure of the catalyst can contain a great amount of α-olefin.Various substituents can be included in a cyclopentadienyl ring and aquinoline-based ring. Thus, the structures and properties of thepolyolefin can be controlled since electronic and steric environments inthe vicinity of the metal can be easily controlled. The transition metalcomplex according to the current embodiment of the present invention maybe used to prepare a catalyst that is used to polymerize olefinmonomers. However, use of the transition metal complex is not limitedthereto.

The transition metal complex represented by Formula 1 may have astructure represented by Formula 2. The compound represented by Formula2 can control electronic and steric environments in the vicinity ofmetal.

Here, R₄s and R₅s are each independently a hydrogen atom; and a C₁₋₂₀alkyl, C₆₋₂₀ aryl or silyl radical;

each of the R₆s are independently a hydrogen atom; a C₁₋₂₀ alkyl orC₆₋₂₀ aryl radical; a C₂₋₂₀ alkenyl, C₇₋₂₀ alkylaryl or C₇₋₂₀ arylalkylradical; and a C₁₋₂₀ C₆₋₂₀ aryloxyl or amido radical, wherein at leasttwo R₆s can be connected to each other to form an aliphatic or aromaticring;

Q₃ and Q₄ are each independently a halogen radical; a C₁₋₂₀ alkylamidoor C₆₋₂₀ arylamido radical; and a C₁₋₂₀ alkyl radical; n is a integersuch as 0 or 1; and

M is a Group 4 transition metal.

The transition metal complex represented by Formula 1 or 2 may be one ofthe compounds represented by the following Formulae. These compounds cancontrol electronic and steric environments in the vicinity of metal.

Here, each of the R₇s are independently a hydrogen atom or a methylradical, and

Q₅ and Q₆ are each independently a methyl, dimethylamido or chlorideradical.

According to another embodiment of the present invention, there isprovided an amine-based compound represented by Formulae 3 and 4 belowas a ligand of the transition metal complex of Formula 1 or 2.

Here, R₁, R₂ and R₃ are as described above.

And, n is a integer such as 0 or 1.

When these ligands are coordinated with metal, a phenylene bridge isformed, and nitrogen and cyclopentadiene are coordinated with metal.These compounds may be used as ligands of the transition metal complex.However, use of the compounds is not limited thereto. That is thecompounds can be used in any applications.

According to an embodiment of the present invention, there is provided acatalyst composition including: a transition metal complex representedby Formula 1 or 2; and at least one cocatalyst compound selected fromthe group consisting of compounds represented by Formulae 5, 6, and 7below.

The catalyst composition may be used for homopolymerization orcopolymerization of olefin.

—[Al(R₈)—O]_(a)—  Formula 5

Here, each of the R₈s are independently a halogen radical; a C₁₋₂₀hydrocarbyl radical; or a C₁₋₂₀ hydrocarbyl radical substituted with ahalogen atom, and a is an integer of 2 or greater.

D(R₈)₃   Formula 6

Here, D is aluminum or boron, and R₈ is as described above.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  Formula 7

Here, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z isa Group 13 atom; and each of the As are independently a C₆₋₂₀ aryl orC₁₋₂₀ alkyl radical in which at least one hydrogen atom is substitutedwith a halogen atom, or a C₁₋₂₀ hydrocarbyl, C₁₋₂₀ alkoxy, or phenoxyradical.

The transition metal complex represented by Formula 1 of the catalystcomposition may be one of the compounds represented by the followingFormulae.

Here, each of the R₇s are independently a hydrogen atom or a metalradical, and Q₅ and Q₆ are each independently a methyl, dimethylamido orchloride radical.

A method of preparing the catalyst composition according to anembodiment of the present invention includes: bringing the transitionmetal complex represented by Formula 1 into contact with a compoundrepresented by Formula 5 or 6 to obtain a mixture; and adding a compoundrepresented by Formula 7 to the mixture.

A method of preparing the catalyst composition according to anotherembodiment of the present invention includes bringing the transitionmetal complex represented by Formula 1 into contact with a compoundrepresented by Formula 7.

In the former method, the molar ratio of the transition metal complex tothe compound represented by Formula 5 or 6 may be in the range of 1:2 to1:5,000, more preferably in the range of 1:10 to 1:1,000, and mostpreferably in the range of 1:20 to 1:500.

Meanwhile, the molar ratio of the transition metal complex to thecompound represented by Formula 7 may be in the range of 1:1 to 1:25,more preferably in the range of 1:1 to 1:10, and most preferably in therange of 1:1 to 1:5.

When the molar ratio of the transition metal complex to the compoundrepresented by Formula 5 or 6 is less than 1:2, the metal compound isinsufficiently alkylated since the amount of an alkylating agent is toosmall. On the other hand, when the molar ratio of the transition metalcomplex to the compound represented by Formula 5 or 6 is greater than1:5,000, the metal compound is alkylated, but excess alkylating agentcan react with the activator of Formula 7 so that the alkylated metalcompound is less activated. When the molar ratio of the transition metalcomplex to the compound represented by Formula 7 is less than 1:1, theamount of the activator is relatively small so that the metal compoundis less activated. On the other hand, when the molar ratio of thetransition metal complex to the compound represented by

Formula 7 is greater than 1:25, the metal compound may be completelyactivated but excess activator remains, that is, the preparation processfor the catalyst composition is expensive, and the obtained polymerpurity is poor.

In the latter method, the molar ratio of the transition metal complex tothe compound represented by Formula 7 may be in the range of 1:10 to1:10,000, more preferably in the range of 1:100 to 1:5,000, and mostpreferably in the range of 1:500 to 1:2,000. When the molar ratio of thetransition metal complex to the compound represented by Formula 7 isless than 1:10, the metal compound is insufficiently alkylated since theamount of an alkylating agent is relatively small. On the other hand,when the molar ratio of the transition metal complex to the compoundrepresented by Formula 7 is greater than 1:10,000, the metal compoundmay be completely activated but excess activator remains, that is, thepreparation process for the catalyst composition is expensive, and theobtained polymer purity is poor.

A reaction solvent used in the preparation of the activated catalystcomposition may be a hydrocarbon solvent such as pentane, hexane, orheptane, or an aromatic solvent such as benzene and toluene, but is notlimited thereto and any solvent that is used in the art can be used.

In addition, the transition metal complex represented by Formula 1 or 2and the cocatalyst may be loaded on silica or alumina.

The compound represented by Formula 5 may be an alkylaluminoxane, morepreferably one of methylaluminoxane, ethylaluminoxane,isobutylaluminoxane, and butylaluminoxane, and most preferablymethylaluminoxane.

The compound represented by Formula 6 may be one of trimethylaluminum,triethylaluminum, triisobutylaluminum, tripropylaluminum,tributylaluminum, dimethylchloroaluminum, triisopropylaluminum,tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum,triisopentylaluminum, trihexylaluminum, trioctylaluminum,ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum,tri-p-tolylaluminum, dimethylaluminummethoxide,dimethylaluminumethoxide, trimethylboron, triethylboron,triisobutylboron, dripropylboron, and tributylboron, and more preferablytrimethylaluminum, triethylaluminum, or triisobutylaluminum, but is notlimited thereto.

Examples of the compound represented by Formula 7 may includetriethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron,trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron,trimethylammoniumtetra(p-tolyl)boron,trimethylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,trimethylammoniumtetra(p-trifluoromethylphenyl)boron,tributylammoniumtetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylanilinium tetraphenylboron,N,N-diethylanilinium tetrapentafluorophenylboron,diethylammoniumtetrapentafluorophenylboron,triphenylphosphoniumtetraphenylboron,trimethylphosphoniumtetraphenylboron,triethylammoniumtetraphenylaluminum,tributylammoniumtetraphenylaluminum,trimethylammoniumtetraphenylaluminum,tripropylammoniumtetraphenylaluminum,trimethylammoniumtetra(p-tolyl)aluminum,tripropylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum,tributylammoniumtetra(p-trifluoromethylphenyl)aluminum,trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum, tributylammoniumtetrapentafluorophenylaluminum,N,N-diethylaniliniumtetraphenylaluminum,N,N-diethylaniliniumtetraphenylaluminum,N,N-diethylaniliniumtetrapentafluorophenylaluminum,diethylammoniumtetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum,trimethylphosphoniumtetraphenylaluminum,triethylammoniumtetraphenylaluminum,tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylboron,tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron,tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,trimethylammoniumtetra(p-trifluoromethylphenyl)boron,tributylammoniumtetrapentafluorophenylboron,N,N-diethylaniliniumtetraphenylboron,N,N-diethylaniliniumtetraphenylboron,N,N-diethylaniliniumtetrapentafluorophenylboron,diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron,triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, andtriphenylcarboniumtetrapentafluorophenylboron.

According to an embodiment of the present invention, there is provided amethod of synthesizing an olefin polymer using the catalyst composition.

In the method, the catalyst composition including a transition metalcomplex represented by Formula 1 or 2 and at least one compound selectedfrom the group consisting of compounds represented by Formulae 5, 6, and7 is brought into contact with an olefin-based monomer to prepare apolyolefin homopolymer or copolymer.

The transition metal complex that is used in the method of preparing thehomopolymer or copolymer may be represented by one of the followingFormulae.

Here, each of the R₇s are independently a hydrogen atom or a methylradical, and

Q₅ and Q₆ are each independently a methyl, dimethylamido or chlorideradical.

A polymerization process using the catalyst composition may be asolution process, but when the catalyst composition is used togetherwith an inorganic support, such as silica, the polymerization processcan also be a slurry or gas phase process.

In the method, the catalyst composition may be dissolved or diluted in asolvent suitable for olefin polymerization, before being used. Examplesof the solvent may include a C₅₋₁₂ aliphatic hydrocarbon solvent such aspentane, hexane, heptane, nonane, decane, and derivatives thereof; anaromatic hydrocarbon solvent such as toluene or benzene; and ahydrocarbon solvent substituted with a chlorine atom such asdichloromethaneor chlorobenzene. The solvent may be treated with a smallamount of alkylaluminum to eliminate a small amount of water and airwhich poison the catalyst composition, or a cocatalyst can further beused.

Examples of the olefin-based monomer which is polymerized using themetal complexes and the cocatalysts may include α-olefin and a cyclicolefin. A diene olefin-based monomer or a triene olefin-based monomerwhich have at least two double bonds may also be polymerized. Examplesof the olefin-based monomer or triene olefin-based monomer may includeethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene,1-hexadecene and 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinyl norbornene, dicyclopentadiene,1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene,divinylbenzene, and 3-chloromethyl styrene. More than two of themonomers may be mixed and copolymerized.

In particular, the catalyst composition according to an embodiment ofthe present invention is used to copolymerize ethylene and 1-octenehaving large steric hindrance at a high reaction temperature of 90° C.or higher to thereby obtain a copolymer having high molecular weight buthaving a very low density less than 0.910 g/cc.

According to an embodiment of the present invention, there is providedan olefin polymer prepared using a method of synthesizing an olefin

The olefin polymer may be a homopolymer or a copolymer. When the olefinpolymer is a copolymer of ethylene and a comonomer, the monomer may beat least one copolymer selected from the group consisting of ethylene,propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

The present invention will be described in greater detail with referenceto the following examples. The following examples are for illustrativepurposes only and are not intended to limit the scope of the invention.

Synthesis of Ligands and Transition Metal Complexes

Organic reagents and solvents were obtained from Aldrich Co., Inc. andMerck Co., Inc. and purified using a standard method. Each process forthe synthesis was performed while isolated from air and moisture toimprove reproducibility of experiments. The structure of compoundsproduced in the following examples was identified using a 400 MHznuclear magnetic resonance (NMR) and an X-ray spectrometer.

EXAMPLE 1 5-bromo-7-methyl-1,2,3,4-tetrahydroquinoline

1.16 g (7.90 mmol) of 6-methyl-1,2,3,4-tetrahydroquinoline was dissolvedin 4 ml of carbon tetrachloride and the solution was cooled to −20° C.1.41 g (7.90 mml) of solid-state N-bromosuccinimide was slowly added tothe solution and the resultant mixture was reacted at room temperaturefor 5 hours. The product was filtered using a column chromatography witha MC/hexane (v:v=1:1) solvent, and 0.71 g of pale yellow oil wasobtained (40%).

¹H NMR (C₆D₆): δ 1.42-1.52 (m, 2H, CH₂), 2.00 (s, 3H, CH₃), 2.39 (t,J=6.4 Hz, 2H, CH₂), 2.75 (dt, J=2.8, 8.4 Hz, 2H, N—CH₂), 4.04 (br s, 1H,NH), 6.51 (s, 1H, C₆H₂), 7.09 (s, 1H, C₆H₂) ppm. ¹³C{¹H} NMR(C₆D₆): δ20.06, 22.04, 27.60, 41.91, 108.84, 122.59, 126.16, 129.48, 130.67,139.79 ppm. Anal._Calc. (C₁₀H₁₂BrN): C, 53.12; H, 5.35; N, 6.19%. Found:C, 53.30; H, 5.13; N, 6.51%.

EXAMPLE 25-(3,4-dimethyl-2-cyclopentene-1-one)-7-methyl-1,2,3,4-tetrahydroquinoline

1.27 g (8.26 mmol) of2-(dihydroxyboryl)-3,4-dimethyl-2-cyclopentene-1-one, 1.25 g (11.8 mmol)of Na₂CO₃, 0.182 g (0.157 mmol) of Pd(PPh₃)₄, (Ph: phenyl group) and7.87 mmol of 5-bromo-7-methyl-1,2,3,4-tetrahydroquinoline were mixed. 21ml of degassed dimethylether (DME) and 7 ml of distilled water wereadded to the mixture. The resultant mixture was heated at 95° C.overnight. The reaction mixture was cooled to room temperature, andabout twice extracted with 50 ml of ethylacetate. The product wasfiltered using a column chromatography with a hexane/ethylacetate(v:v=2:1) solvent, and a pale yellow solid product was obtained (90%).

¹H NMR (C₆D₆): δ 0.77 (d, J=7.2 Hz, 3H, CH₃), 1.59-1.70 (m, 2H,CH₂CH₂CH₂), 1.65 (s, 3H, CH₃), 1.84 (dd, J=2.4, 18.4 Hz, 1H, OCCH₂),2.21 (s, 3H, CH₃), 2.20-2.30 (m, 1H, CH), 2.44 (dd, J=6.4, 18.4 Hz, 1H,OCCH₂), 2.60 (br t, J=6 Hz, 2H, CH₂), 2.97 (br t, J=5.6 Hz, 2H, N—CH₂),4.06 (s, 1H, NH), 6.66 (s, 1H, CH, C₆H₂), 6.74 (s, 1H, C₆H₂) ppm.¹³C{¹H} NMR(C₆D₆): δ 15.83, 19.06, 20.58, 22.51, 27.92, 37.52, 42.48,43.55 ppm. Anal. Calc. (C₁₇H₂₁NO): C, 79.96; H, 8.29; N, 5.49%. Found:C, 80.17; H, 8.44; N, 5.75%.

EXAMPLE 35-(2,3,5-trimethyl-1,3-cyclopentadienyl)-7-methyl-1,2,3,4-tetrahydroquinoline

21.4 mmol of anhydrous La(OTf)₃, (Tf: triflate) was mixed with 24 ml oftetrahydrofuran (THF) and the mixture was cooled to −78° C. 13.4 ml(21.4 mmol) of MeLi (Me: methyl) was added to the mixture and reactedfor about 1 hour. 7.13 mmol of5-(3,4-dimethyl-2-cyclopentene-1-one)-7-methyl-1,2,3,4-tetrahydroquinolinewas added to the mixture and reacted at −78° C. for 2 hours. Theresultant mixture was extracted using water and acetate. The obtainedorganic layer was added to 20 ml (2N) of HCl and the mixture was shakenfor 2 minutes. The resultant mixture was neutralized with 20 ml ofNaHCO₃ water solution and dried with MgSO₄. The product was filteredusing a column chromatography with hexane/ethylacetate (v:v=10:1)solvent, and a pale yellow solid product was obtained (40%).

¹H NMR (C₆D₆): δ 1.66-1.71 (m, 2H, CH₂CH₂CH₂), 1.80 (s, 3H, CH₃), 1.89(s, 3H, CH₃), 1.90 (s, 3H, CH₃), 2.24 (s, 3H, CH₃), 2.64 (br t, J=6.4Hz, 2H, CH₂), 2.74 (d, J=2 Hz, 2H, CH₂), 2.86-2.92 (m, 2H, N—CH₂), 3.62(br s, 1H, NH), 6.75 (s, 1H, C₆H₂), 6.77 (s, 1H, C₆H₂) ppm. ¹³C{¹H}NMR(C₆D₆): δ 11.85, 13.61, 14.39, 20.74, 22.86, 27.70, 42.20, 48.88,120.81, 122.01, 124.78, 128.68, 129.36, 132.87, 136.36, 136.65, 140.75,141.15 ppm.

EXAMPLE 4([(7-Methyl-1,2,3,4-tetrahydroquinolin-8-yl)trimethylcyclopentadienyl-eta5,kapa-N]titanium bis(dimethylamide)) compound

0.696 mmol of5-(2,3,5-trimethyl-1,3-cyclopentadienyl)-7-methyl-1,2,3,4-tetrahydroquinolineligand and 0.156 g (0.696 mmol) of Ti(NMe₂)₄ were dissolved in 2 ml oftoluene. The mixture was reacted at 80° C. for two days. After thesolvents were eliminated, a red solid product was obtained (100%). Theobtained titanium compound was identified through ¹H-NMR spectroscope.

¹H NMR (C₆D₆): δ1.69-1.74 (m, 2H, CH₂CH₂CH₂), 1.86 (s, 3H, CH₃), 1.88(s, 3H, CH₃), 1.92 (s, 3H, CH₃), 2.31(s, 3H, CH₃), 2.57 (t, J=5.6 Hz,2H, CH₂), 2.95 (s, 6H, NCH₃), 3.27 (s, 6H, NCH₃), 4.02 (ddd, J=5.2, 7.2,12.0 Hz, 1H, NCH₂), 4.24 (dt, J=5.2, 12.4 Hz, 1H, NCH₂), 5.78 (s, 1H,Cp-H), 6.77 (s, 1H, C₆H₂), 6.91 (s, 1H, C₆H₂) ppm.

EXAMPLE 5([(7-Methyl-1,2,3,4-tetrahydroquinolin-8-yl)trimethylcyclopentadienyl-eta5,kapa-N]titanium dichloride) compound

2 ml of toluene was added to the bis(dimethylamido)titanium compoundthat was obtained in Example 4. 0.269 g (2.09 mmol) of Me₂SiCl₂ wasadded to the mixture at room temperature and the mixture was reacted forabout 4 hours. The obtained product was recrystallized in hexane at −30°C. and 0.183 g of a pure red solid product was obtained (66%).

¹H NMR (C₆D₆): δ1.36-1.44 (m, 2H, CH₂CH₂CH₂), 1.76 (s, 3H, CH₃), 1.85(s, 3H, CH₃), 2.07 (s, 3H, CH₃), 2.18 (s, 3H, CH₃), 2.12 (t, J=4 Hz, 2H, CH₂), 4.50-4.70 (m, 2H, N—CH₂), 6.02 (s, 1H, Cp-H), 6.59 (s, 1H,C₆H₂), 6.78 (s, 1H, C₆H₂) ppm. ¹³C{¹H} NMR (C₆D₆): 12.76, 14.87, 15.06,21.14, 22.39, 26.32, 54.18, 117.49, 120.40, 126.98, 129.53, 130.96,131.05, 133.19, 143.22, 143.60, 160.82 ppm. Anal. Calc. (C₁₈H₂₁Cl₂NTi):C, 58.41; H, 5.72; N, 3.78%. Found: C, 58.19; H, 5.93; N, 3.89%.

EXAMPLE 65-(tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

957 mg (7.185 mmol) of 1,2,3,4-tetrahydroquinoline was dissolved in 10ml of THF, and stirred at −78° C. for 30 minutes. 2.87m1 (7.185mmol) ofnBuLi was added thereto using a syringe under a nitrogen atmosphere(yellow suspension). The mixture was sufficiently stirred for 3 hours,and the temperature was increased to −20° C. to eliminate the gas. Thetemperature was cooled again to −78° C. and CO₂ was injected to themixture (The color of the mixture turned to colorless white). Thetemperature was increased to −20° C. and the remaining CO₂ waseliminated in vacuum for 1 hour. Then, 5.07 ml (8.622 mmol) oftert-butyllitium (BuLi) was added to the mixture (The color of themixture turned to red). While the temperature was maintained at −20° C.,the mixture was sufficiently stirred for 2 hours, and 26.1 ml (8.622mmol) of 0.33 M CeCl₃:2LiCl solution dissolved in THF and 1.182 g (8.622mmol) of tetramethyl cyclopentenone were added to the mixture under anitrogen atmosphere. While the temperature was gradually increased toroom temperature, the solvents were eliminated by venting. Then, themixture was titurated using pentane under a nitrogen atmosphere andfiltered to obtain a white crystalline powder (41%).

¹H NMR(C6D6):δ 1.00(d, J=6.4 Hz, 3H, Cp-CH₃), 1.66-1.74(m, 2H,quinoline-CH₂), 2.64(t, J=6.0 Hz, 2H, quinoline-CH₂), 2.78-2.98(m, 2H,quinoline-CH₂), 3.05(br s, 1H, Cp-H), 3.76(br s, 1H, N—H), 6.76(t, J=7.2Hz, 1H, quinoline-CH), 6.91(d, J=5.6 Hz, 1H, quinoline-CH), 6.93(d,J=7.2 Hz, 1H, quinoline-CH)ppm

EXAMPLE 7([(1,2,3,4-Tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titaniumdimethyl) compound

220 mg (0.792 mmol) of 2.5 M n-butyllitium (n-BuLi) was gradually addedto a cold (−30° C.) solution of 100 mg (0.396 mmol) of the obtainedcompound in Example 6 dissolved in ether while stirring. The temperatureof the mixture was increased to room temperature. The resultant mixturewas reacted for 6 hours, filtered, and washed several times with ether.Then the ether was evaporated in vacuum to obtain 90 mg of a pale yellowsolid product (dilithium salt compound). It was identified that 0.43equivalent of ether was coordinated (77%) through ¹H NMR and ¹³C NMRspectroscope.

¹H NMR(C6D6):δ 2.03(br s, 2H, Quinoline-CH₂), 2.16(br s, 12H, Cp-CH₃),3.14(br s, 2H,Qnoline-CH₂), 3.85(br s, 2H, Quinoline-CH₂), 6.33(t, J=6.4Hz, 1H, Quinoline-CH), 6.95(d, J=0.8 Hz, Quinoline-CH),7.32(br s, 1H,Quinoline-CH)ppm.

66 mg (0.235 mmol) of TiCl4.DME was mixed with ether at −30□ and themixture was placed in a refrigerator for about 1 hour. Then, 3 ml (0.470mmol) of 1.4 M methyllithium (MeLi) was gradually added to the mixturewhile stirring. After stirring for 15 minutes, 70 mg (0.235 mmol) ofdilithium salt compound was added to the mixture. The mixture wasreacted for 3 hours while stirring at room temperature. Then the solventwas evaporated in vacuum and the mixture was dissolved in pentane andfiltered. The pentane in the resultant mixture was evaporated under avacuum, and thus 52 mg of dark brown titanium complex was obtained(67%).

¹H NMR(C6D6):δ 7.00 (d, J=7.6 Hz, 1H), 9.92 (d, J=7.6 Hz, 1H), 6.83 (t,J=7.6 Hz, 1H), 4.53 (m, 2H), 2.47 (t, J=6.4 Hz, 2H), 2.05 (s, 6H), 1.66(s, 6H), 1.76-1.65 (m, 2H), 0.58 (s, 6H).

EXAMPLE 8 5-Indenyl-1,2,3,4-tetrahydroquinoline

Yellow oil was obtained in the same manner as in Example 6, except thatindenone was used instead of tetramethyl cyclopentenone and the productwas filtered using a column chromatography with a hexane/ethyl acetate(v:v=20:1) solvent (Yield: 49%).

¹H NMR(C6D6): δ 1.58-1.64 (m, 2H, quin-CH₂), 2.63 (t, J=6.8 Hz, 2H,quin-CH₂), 2.72-2.77 (m, 2H, quin-CH₂), 3.17 (d, J=2.4 Hz, 2H,indenyl-CH₂), 3.85 (br s, 1H, N—H), 6.35 (t, J=2.0 Hz, 1H, indenyl-CH),6.76 (t, J=7.6 Hz, 1H, quin-CH), 6.98 (d, J=7.2 Hz, 1H, quin-CH), 7.17(td, J=1.6, 7.2 Hz, 1H, quin-CH), 7.20 (td, J=1.6, 7.2 Hz, 2H,indenyl-CH), 7.34 (d, J=7.2 Hz, 1H, indenyl-CH), 7.45 (dd, J=1.2, 6.8Hz, 1H, indenyl-CH)ppm. ¹³C NMR(C6D6): δ 12.12, 23.08, 27.30, 48.84,51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm.

EXAMPLE 9 [(1,2,3,4-Tetrahydroquinolin-8-yl)indenyl-eta5,kapa-N]titaniumdimethyl

A dilithium salt compound was obtained in the same manner as in Example7 using 5-indenyl-1,2,3,4-tetrahydroquinoline (Yield: 95%).

¹H NMR(C6D6): δ 2.02 (t, J=4.8 Hz, 2H, quin-CH₂), 3.15 (t, J=5.6 Hz, 2H,quin-CH₂), 3.94 (br s, 2H, quin-CH₂), 6.31 (t, J=7.2 Hz, 1H,indenyl-CH), 6.76-6.83 (m, 2H, quin-CH), 6.99 (t, J=7.2, 2.0 Hz, 2H,quin-CH), 7.48 (d, J=7.2 Hz, 2H, indenyl-CH), 8.02 (t, J=8.0 Hz, 2H,indenyl-CH) ppm.

A titanium compound was prepared using the obtained dilithium saltcompound in the same manner as in Example 7 (Yield: 47%).

¹H NMR(C6D6): δ-0.01 (s, 3H, Ti—CH₃), 0.85 (s, 3H, Ti—CH₃), 1.56-1.68(m, 2H, quin-CH₂), 2.43 (t, J=6.4 Hz, 2H, quin-CH₂), 6.30 (d, J=3.6 Hz,1H, indenyl-CH), 6.61 (d, J=3.6 Hz, 1H, indenyl-CH), 6.70 (ddd, J=0.8,6.8, 8.4 Hz, 1H, indenyl-CH), 6.85 (t, J=7.6 Hz, 1H, quin-CH), 6.95 (tt,J=0.8, 6.8 Hz, 1H, quin-CH), 7.01 (tdd, J=0.8, 6.8, 8.4 Hz, 2H,indenyl-CH), 7.13-7.17 (m, 1H, quin-CH), 7.48 (d, J=8.4 Hz, 1H,indenyl-CH) ppm. ¹³C NMR(C6D6): δ 22.83, 27.16, 49.35, 55.12, 58.75,103.36, 119.63, 120.30, 123.18, 125.26, 125.60, 127.18, 127.36, 127.83,129.13, 129.56, 135.10, 161.74ppm.

EXAMPLE 10 5-Fluorenyl-1,2,3,4-tetrahydroquinoline

A yellow solid compound was obtained in the same manner as in Example 6,except that fluorenone was used instead of tetramethyl cyclopentenoneand the product was filtered using a column chromatography with ahexane/ethyl acetate (v:v=20:1) solvent and recrystallized in diethylether (Yield: 56%).

¹H NMR(C6D6): δ 1.20 (t, J=7.6 Hz, 2H, quin-CH₂), 1.71 (s, 1H, xx), 2.29(s, 2H, quin-CH₂), 2.38(t, J=6.0 Hz, 2H, quin-CH₂), 2.64 (s, 1H,quin-CH₂), 2.72 (s, 2H, quin-CH₂), 2.30 (s, 1H, N—H), 3.82 (s, 0.5H,N—H), 4.81 (s, 1H, quin-CH), 6.42 (d, J=7.2 Hz, 2H, quin-CH), 6.81 (t,J=7.2 Hz, 1H, quin-CH), 6.94 (dd, J=1.2, 7.2 Hz, 1H, quin-CH), 7.10 (d,J=7.6 Hz, 2H, fluorenyl-CH), 7.23 (t, J=7.2 Hz, 2H, fluorenyl-CH),7.32(d, J=7.6 Hz, 2H, fluorenyl-CH), 7.42 (d, J=6.8 Hz, 1H, quin-CH),7.67 (d, J=7.2 Hz, 2H, fluorenyl-CH)ppm.

EXAMPLE 11[(1,2,3,4-Tetrahydroquinolin-8-yl)fluorenyl-eta5,kapa-N]titaniumdimethyl

A dilithium salt compound was obtained in the same manner as in Example7 using 5-fluorenyl-1,2,3,4-tetrahydroquinoline (Yield: 94%).

¹H NMR(C6D6): δ 2.17 (s, 2H, quin-CH₂), 3.29-2.26 (m, 2H, quin-CH₂),4.11(br s, 2H, quin-CH₂), 6.31 (t, J=7.2 Hz, 1H, quin-CH), 6.91 (t,J=7.6 Hz, 2H, fluorenyl-CH), 6.99 (d, J=7.2 Hz, 1H, quin-CH), 7.12 (t,J=6.8 Hz, 2H, fluorenyl-CH), 7.58 (dd, J=1.2, 7.6 Hz, 1H, quin-CH), 8.15(d, J=8.0 Hz, 2H, fluorenyl-CH), 8.57(d, J=8.0 Hz, 2H, fluorenyl-CH)ppm.

A titanium compound was prepared using the obtained dilithium saltcompound in the same manner as in Example 7 (Yield: 47%).

¹H NMR(C6D6): δ 0.14 (s, 6H, Ti—CH₃), 1.56-1.68 (m, 2H, quin-CH₂), 2.48(t, J=6.4 Hz, 2H, quin-CH₂), 4.18-4.30 (m, 2H, quin-CH₂), 6.88-6.96 (m,3H, CH), 7.04 (d, J=7.6 Hz, 1H, quin-CH), 7.10 (ddd, J=1.2, 6.8, 8.4 Hz,2H, fluorenyl -CH), 7.17 (dd, J=0.8, 8.4 Hz, 2H, fluorenyl-CH), 7.28 (d,J=7.2 Hz, 1H, quin-CH), 7.94 (dd, J=0.8, 8.4 Hz, 2H, fluorenyl-CH) ppm.¹³C NMR(C6D6): δ 14.54, 22.76, 27.26, 48.58, 59.65, 111.21, 118.69,118.98 120.17, 123.34, 123.67, 126.16, 126.42, 127.75, 129.29, 129.41,137.28, 160.63ppm.

EXAMPLE 12 7-(2,3,4,5-Tetramethyl-1,3-cyclopentadienyl)indoline

Yellow oil was obtained in the same manner as in Example 6, except thatindoline was used instead of 1,2,3,4-tetrahydroquinoline and the productwas filtered using a column chromatography with a hexane/ethyl acetate(v:v=20:1) solvent (Yield: 15%).

¹H NMR(C6D6): δ 0.99 (d, J=7.6 Hz, 1H, Cp-CH), 1.82 (s, 3H, Cp-CH₃),1.87 (s, 6H, Cp-CH₃), 2.68-2.88 (m, 2H, ind-CH₂), 2.91-2.99 (m , 1H,Cp-CH), - 3.16 (m, 3H, ind-CH₂ N—H), 6.83 (t, J=7.4 Hz, 1H, ind-CH),6.97 (d, J=7.6 Hz, 1H, ind-CH), 7.19 (d, J=6.8 Hz, 1H, ind-CH) ppm.

EXAMPLE 13[(Indolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl

A titanium compound was prepared using7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline in the same manneras in Example 7 (Yield: 71%).

¹H NMR(C6D6): δ 0.69 (s, 6H, Ti—CH₃), 1.71 (s, 6H, Cp-CH₃), 2.04 (s, 6H,Cp-CH₃), 2.73 (t, J=8.0 Hz, 2H, ind-CH₂), 4.67 (t, J=8.0 Hz, 2H,ind-CH₂), 6.82 (t, J=7.2 Hz, 1H, ind-CH), 7.00 (t, J=7.2 Hz, 2H, ind-CH)ppm. ¹³C NMR(C6D6): δ 12.06, 12.15, 32.24, 54.98, 56.37, 120.57, 120.64,121.54, 124.02, 126.52, 126.81, 136.75ppm.

EXAMPLE 142-Methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

2-Methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline was obtained in the same manner as in Example 6, except that 5.02 g(34.1 mmol) of 1,2,3,4-tetrahydroquinaldine was used instead of1,2,3,4-tetrahydroquinoline (Yield: 51%).

¹H NMR(CDCl₃): δ 6.89(d, J=7.2 Hz, 1H, CH), δ 6.74(d, J=7.2 Hz, 1H, CH),δ 6.57(t, J=7.4 Hz, 1H, CH), δ 3.76(br s, 1H, NH), δ 3.45(br s, 1H,Cp-CH), δ 3.32(m, 1H, quinoline-CH), δ 3.09-2.70(m, 2H, quinoline-CH₂),δ 1.91(s, 3H, Cp-CH₃), δ 1.87(s, 3H, Cp-CH₃), δ 1.77(s, 3H, Cp-CH₃), δ1.67-1.50(m, 2H, quinoline-CH₂), 1.17(d, J=6.4 Hz, 3H, quinoline-CH₃), δ0.93(d, J=7.6 Hz, 3H, Cp-CH₃) ppm.

EXAMPLE 15 [(2- Methyl-1,2 ,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopenta-dienyl-etas, kapa-N]titanium dimethyl

4.92 g of pale yellow solid (dilithium salt compound) to which 1.17equivalent of diethyl ether was coordinated was obtained in the samemanner as in Example 7 using 4.66 g (17.4 mmol) of2-methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (Yield: 77%).

¹H NMR(Pyridine-d8): δ 7.37(br s, 1H, CH), δ 7.05(d, J=6 Hz, 1H, CH), δ6.40(t, J=6.8 Hz, 1H, CH), δ 3.93(br s, 1H, CH), δ 3.27(m, 1H, CH), δ3.06(m, 1H, CH), δ 2.28-2.07(m, 12H, Cp-CH₃), δ 1.99(m, 1H, CH), δ1.78(m, 1H, CH), δ 1.18(d, J=5.6 Hz, quinoline-CH₃) ppm.

0.56 g of a titanium compound was prepared in the same manner as inExample 7using 1.00 g (2.73 mmol) of the obtained dilithium saltcompound (Yield: 60%).

¹H NMR(CDCl₃): δ 6.95(d, J=8 Hz, 1H, CH), δ 6.91(d, J=8 Hz, 1H, CH), δ6.73(t, J=8 Hz, 1H, CH), δ 5.57(m, 1H, CH), δ 2.83(m, 1H, CH), δ 2.55(m,1H, CH), δ 2.24(s, 3H, Cp-CH₃), δ 2.20(s, 3H, Cp-CH₃), δ 1.94-1.89(m,1H, CH), δ 1.83-1.75(m,1H, CH), δ 1.70(s, 3H, Cp-CH₃), δ 1.60(s, 3H,Cp-CH₃), δ 1.22(d, J=6.8 Hz, 3H, quinoline-CH₃), δ 0.26(d, J=6.8 Hz, 6H,TiMe₂-CH₃) ppm.

EXAMPLE 166-Methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

6-Methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinolinewas obtained in the same manner as in Example 6 except that 5.21 g (35.4mmol) of 6-methyl-1,2,3,4-tetrahydroquinoline was used instead of1,2,3,4-tetrahydroquinoline (Yield: 34%).

¹H NMR(CDCl₃): δ 6.70(s, 1H, CH), δ 6.54(s, 1H, CH), δ 3.71(br s, 1H,NH), δ 3.25-3.05(m, 3H, Cp-CH, quinoline-CH₂), δ 2.76(t, J=6.4 Hz, 2H,quinoline-CH₂), δ 2.19(s, 3H, CH₃), δ 1.93-1.86(m, 2H, quinoline-CH₂), δ1.88(s, 3H, Cp-CH₃), δ 1.84(s, 3H, Cp-CH₃), δ 1.74(s, 3H, Cp-CH₃), δ0.94(br d, J=6.8 Hz, 3H, Cp-CH₃) ppm.

EXAMPLE 17[(6-Methyl-1,2,3,4-tetrahydroquinolin-8-yptetramethylcyclopenta-dienyl-etas,kapa-N]titanium dimethyl

2.56 g of pale yellow solid (dilithium salt compound) to which 1.15equivalent of diethyl ether was coordinated was obtained in the samemanner as in Example 7 using 3.23 g (12.1 mmol) of6-methyl-8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline(Yield: 58%).

¹H NMR(Pyridine-d8): δ 7.02(br s, 1H, CH), δ 6.81(s, 1H, CH), δ 3.94(m,2H, CH₂), δ 3.19(m, 2H, CH₂), δ 2.52-2.10(m, 17H, CH₂, quinoline-CH₃,Cp-CH₃) ppm,

0.817 g of a titanium compound (58%) was prepared in the same manner asin Example 7 using 1.50 g (4.12 mmol) of the obtained dilithium saltcompound.

¹H NMR(C₆D₆): δ 6.87(s, 1H, CH), δ 6.72(s, 1H, CH), δ 4.57(m, 2H, CH₂),δ 2.45(t, J=6.2 Hz, 2H, CH₂), δ 2.24(s, 3H, quinoline-CH₃), δ 2.05(s,6H, Cp-CH₃), δ 1.72-1.66(m, 2H, CH₂), δ 1.69(s, 6H, Cp-CH₃), δ 0.57(s,6H, TiMe₂-CH₃) ppm.

EXAMPLE 18 2-Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

2-Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline wasobtained in the same manner as in Example 6, except that 6.23 g (46.8mmol) of 2-methylindoline was used instead of1,2,3,4-tetrahydroquinoline (Yield: 19%).

¹H NMR(CDCl₃): δ 6.97(d, J=7.2 Hz, 1H, CH), δ 6.78(d, J=8 Hz, 1H, CH), δ6.67(t, J=7.4 Hz, 1H, CH), δ 3.94(m, 1H, quinoline-CH), δ 3.51(br s, 1H,NH), δ 3.24-3.08(m, 2H, quinoline-CH₂, Cp-CH), δ 2.65 (m, 1H,quinoline-CH₂), δ 1.89(s, 3H, Cp-CH₃), δ 1.84(s, 3H, Cp-CH₃), δ 1.82(s,3H, Cp-CH₃), δ 1.13(d, J=6 Hz, 3H, quinoline-CH₃), δ 0.93(3H, Cp-CH₃)ppm.

EXAMPLE 19[(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titaniumdimethyl

A dilithium salt compound to which 0.58 equivalent of diethyl ether wascoordinated was obtained in the same manner as in Example 7 using 2.25 g(8.88 mmol) of2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (1.37 g,Yield: 50%).

¹H NMR(Pyridine-d8): δ 7.22(br s, 1H, CH), δ 7.18(d, J=6 Hz, 1H, CH), δ6.32(t, 1H, CH), δ 4.61(br s, 1H, CH), δ 3.54(m, 1H, CH), δ 3.00(m, 1H,CH), δ 2.35-2.12(m ,13H, CH, Cp-CH₃), δ 1.39(d, indoline-CH₃) ppm.

A titanium compound was prepared using 1.37 g (4.44 mmol) of theobtained dilithium salt compound in the same manner as in Example 7.

¹H NMR(C₆D₆): δ 7.01-6.96(m, 2H, CH), δ 6.82(t, J=7.4 Hz, 1H, CH), δ4.96(m, 1H, CH), δ 2.88(m, 1H, CH), δ 2.40(m, 1H, CH), δ 2.02(s, 3H,Cp-CH₃), δ 2.01(s, 3H, Cp-CH₃), δ 1.70(s, 3H, Cp-CH₃), δ 1.69(s, 3H,Cp-CH₃), δ 1.65(d, J=6.4 Hz, 3H, indoline-CH₃), δ 0.71(d, J=10 Hz, 6H,TiMe₂-CH₃) ppm.

COMPARATIVE EXAMPLE 1

Dimethylsilyl(t-butylamido)(tetramethylcyclopentadienyl)titaniumdichlorideDimethylsilyl(t-butylamido)(tetramethylcyclopentadienyl)titaniumdichloride was purchased from Boulder Scientific, Inc. (U.S.A.) anddirectly used for the ethylene copolymerization.

Ethylene Copolymer

Example 20 Copolymerization of low-pressure ethylene and 1-hexene 30 mlof toluene and 0.3 M 1-hexene was added to a 250 ml Endrew reactor, andthe reactor was preheated to a temperature of 90° C. 0.5 μmol oftitanium transition metal complex prepared in Example 5 treated with 200μmol of triisobutylaluminum compound and 2 μmol of trityltetrakis(pentafluorophenyl)borate cocatalyst were sequentially added tothe reactor. Then copolymerization was performed for 5 minutes, and then4 bar of ethylene pressure was added to the catalyst tank. The remainingethylene was eliminated and the polymer solution was added to excessethanol to induce a precipitation. The obtained polymer was washed withethanol and acetone two to three times, respectively, and the resultantwas dried at 80° C. for over 12 hours in a conventional oven. Example 21Copolymerization of high-pressure ethylene and 1-butene 1.0 L of hexanesolvent and an appropriate amount of 1-butene comonomer was added to a 2L autoclave reactor. The reactor was heated to 90° C., and the reactorwas filled with 20 bar of ethylene. 2 μmol of titanium transition metalcomplex prepared in Example 5 treated with 100 μmol oftriisobutylaluminum compound and 10 μmol of dimethylaniliniumtetrakis(pentafluorophenyl)borate cocatalyst were sequentially added toa catalyst injecting cylinder and injected into the reactor.Polymerization was performed for 10 minutes by continuously injectingethylene in order to maintain the pressure of the reactor between 19 barto 20 bar. Heat generated from the reaction was removed through coolingcoil installed in the reactor and the temperature was maintained asconstant as possible. After the polymerization, the polymer solution wasdischarged to the lower portion of the reactor and cooled using excessethanol. The obtained polymer was dried for over 12 hours in aconventional oven.

Example 22 Copolymerization of high-pressure ethylene and 1-octene 1.0 Lof hexane solvent and an appropriate amount of 1-octene was added to a 2L autoclave reactor. The reactor was preheated to 160° C., and wasfilled with ethylene at a pressure of 28 bar. 5.0 μmol of titaniumtransition metal complex prepared in Example 5 treated with 1.25 μmmolof triisobutylaluminum compound and 25 μmol of trityltetrakis(pentafluorophenyl)borate cocatalyst were sequentially added toa 25 ml catalyst storing tank and filled. Polymerization was performedfor 10 minutes while 40 bar of ethylene was added to the catalyst tank.The remaining ethylene was eliminated and the polymer solution was addedto excess ethanol to induce a precipitation. The obtained polymer waswashed with ethanol and acetone two to three times, respectively, andthe resultant was dried at 80° C. for over 12 hours in a conventionaloven.

Example 23 Copolymerization of high-pressure ethylene and 1-butene 1.0 Lof hexane solvent and an appropriate amount of 1-butene comonomer wasadded to a 2 L autoclave reactor. The reactor was heated to 150° C., andthe reactor was filled with 35 bar of ethylene. 1.0 μmol (Al/Ti=25) oftitanium transition metal complex treated with an appropriate amount oftriisobutylaluminum compound and dimethylaniliniumtetrakis(pentafluorophenyl)borate cocatalyst (B/Ti=5) were sequentiallyadded to a catalyst injecting cylinder and injected into the reactor.Polymerization was performed for 10 minutes by continuously injectingethylene in order to maintain the pressure of the reactor between 34 barto 35 bar. Heat generated from the reaction was removed through coolingcoil installed in the reactor and the temperature was maintained asconstant as possible. After the polymerization, the polymer solution wasdischarged to the lower portion of the reactor and cooled using excessethanol. The obtained polymer was dried for over 12 hours in aconventional oven.

COMPARATIVE EXAMPLE 2

Polymerization was performed in the same manner as in Example 20, exceptthat the transition metal complex prepared in Comparative Example 1 wasused instead of the transition metal complex prepared in Example 5.

COMPARATIVE EXAMPLE 3

Polymerization was performed in the same manner as in Example 21, exceptthat the transition metal complex prepared in Comparative Example 1 wasused instead of the transition metal complex prepared in Example 5.

COMPARATIVE EXAMPLE 4

Polymerization was performed in the same manner as in Example 22, exceptthat the transition metal complex prepared in Comparative Example 1 wasused instead of the transition metal complex prepared in Example 5.

COMPARATIVE EXAMPLE 5

Polymerization was performed in the same manner as in Example 23, exceptthat the transition metal complex prepared in Comparative Example 1 wasused instead of the transition metal complex prepared in Example 5.

Properties Measurement (Weight, Activity, Melt Index, Melting Point, andDensity)

A Melt Index (MI) of the polymers produced in Examples 1-10 andComparative Examples 1-4 was measured using a ASTM D-1238 (Conditions:E, 190° C., 2.16 Kg load). A melting point (T_(m)) of the polymers wasmeasured using a Differential Scanning calorimeter (DSC) 2920 producedby TA Inc. That is, the temperature was increased to 200° C., maintainedat 200° C. for 5 minutes, and decreased to 30° C. Then the temperaturewas increased again and the summit of the DSC curve was measured as themelting point. The temperature was increased and decreased by 10°C./min, and the melting point was obtained in a second temperatureincrease period.

In order to measure the density of the polymers, a sample that had beentreated with 1,000 ppm of an antioxidant was formed into a sheet havinga thickness of 3 mm and a radius of 2 cm by a 180° C. press mold, andthen the prepared sheet was cooled by 10° C./min. The cooled sheet wasmeasured using a Mettler scale.

EXPERIMENTAL EXAMPL 1

The properties of the copolymers prepared in Example 20 and ComparativeExample 2 respectively using the transition metal complexes prepared inExample 5 and Comparative Example 1 were measured according to theexperimental methods described above. The results are presented in Table1.

TABLE 1 Results of copolymerization of ethylene and 1-hexene 1- ActivityBranch hexene (Kg/mmol- Molecular content Catalyst (M) Ti hr) weight^(a)(mol %) Example 20 Example 5 0.3 21 81,000 24 Comparative Comparative0.3 12 113,000 15 Example 2 Example 1 ^(a)weight average molecularweight (Mw)

As shown in Table 1, a degree of copolymerization activity of catalystof Example 5 of the present invention was higher compared to ComparativeExample 1. The molecular weight of the copolymer of Example 20 wasrelatively small; however, the Branch content was very high, and thus itshows that the reactivity of catalyst of Example 5 for the olefinmonomer having large steric hindrance such as 1-hexene is excellent.

EXPERIMENTAL EXAMPLE 2

The properties of the copolymers prepared in Example 21 and ComparativeExample 3 respectively using the transition metal complexes prepared inExample 5 and Comparative Example 1 were measured according to theexperimental methods. The results are presented in Table 2. According tothe content of 1-butene, Example 9 was divided to Examples 21A and 21B.

TABLE 2 Results of copolymerization of ethylene and 1-butene 1-ButeneActivity Melt index^(a) Melt index^(b) Density Catalyst (M) (Kg/mmol-Tihr) (g/10 min) (g/10 min) (g/cc) Example 21A Example 5 0.8 216.0 0 3.620.864 Example 21B Example 5 1.2 280.2 1 27 0.857 Comparative Comparative1.2 340.5 3.10 ∞ 0.878 Example 3 Example 1 ^(a)I₂ value, ^(b)I_(21.6)value

As shown in Table 2, the catalyst of Example 5 of the present inventionhad a lower copolymerization activity than that of Comparative Example 1when ethylene was copolymerized with 1-butene. However, the molecularweight of the copolymer of Examples 21A and 21B was higher than that ofComparative Example 3. According to an embodiment of the presentinvention, the reactivity of catalyst of Example 5 for the olefinmonomer having large steric hindrance such as 1-butene was relativelyexcellent since the density of the copolymer was very low. Inparticular, in Example 21A, even though a smaller amount of 1-butene(0.8 M) was used, a polymer having lower density than ComparativeExample 3 using 1.2 M 1-butene was obtained. Therefore, the catalystaccording to an embodiment of the present invention showed excellentcopolymerization reactivity.

EXPERIMENTAL EXAMPLE 3

The properties of the copolymers prepared in Example 22 and ComparativeExample 4 respectively using the transition metal complexes prepared inExample 5 and Comparative Example 1 were measured according to theexperimental methods descried above. The results are presented in Table3. According to the content of 1-octene, Example 22 was divided toExamples 22A and 22B.

TABLE 3 Results of copolymerization of ethylene and 1-octene Temperature1-octene Activity Melt index^(a) Melting Density Catalyst (° C.) (M)(Kg/mmol-Ti hr) (g/10 min) point(□ (g/cc) Example 22A Example 5 160 0.648.0 6.4 58.6 0.869 Example 22B Example 5 160 0.8 55.6 5.3 49.8 0.864Comparative Comparative 160 0.8 30.4 5.1 98.2 0.904 Example 4 Example 1^(a)I₂ value

As shown in Table 3, the catalyst of Example 5 of the present inventionhad a higher copolymerization activity than that of Comparative Example1 when ethylene was copolymerized with 1-octene. The molecular weight ofthe copolymer of Examples 22A and 22B was similar to that of ComparativeExample 4. The reactivity of the catalyst of Example 5 for the olefinmonomer having large steric hindrance such as 1-octene was relativelyexcellent since the melting point and density of the copolymer was low.In particular, in the present invention, even though a smaller amount of1-octene (0.6 M) was used, a polymer having lower density thanComparative Example 4 using 0.8 M 1-octene was obtained. Therefore, thecatalyst composition according to an embodiment of the present inventionshowed excellent copolymerization reactivity at a high temperature suchas 160° C.

EXPERIMENTAL EXAMPLE 4

The properties of the copolymers prepared in Example 23 and ComparativeExample 5 respectively using the transition metal complexes prepared inExamples 7, 9, 11, 13, 15, 17, 19 and 2 and Comparative Example 1 weremeasured according to the experimental methods. The results arepresented in Table 4.

TABLE 4 Results of copolymerization of ethylene and 1-butene 1-ButeneActivity Melt index^(a) Melt index^(b) Density (M) (kg/mmol-Ti) (g/10min) (g/10 min) (g/cc) Example 23A Example 7 1.6 43.7 3.5 28.8 0.859Example 23B Example 9 1.6 3.4 0 0 0.870 Example 23C Example 11 1.6 16.60 0 0.860 Example 23D Example 13 1.6 15.3 0 0.66 0.873 Example 23EExample 15 1.6 36.0 15.4 ∞ 0.862 Example 23F Example 17 1.6 29.8 1.312.5 0.860 Example 23G Example 19 1.6 22.1 0 0.8 0.873 ComparativeComparative 1.6 30.5 5.9 59 0.900 Example 5A Example 1 Example 23HExample 2^(c) 1.2 57.5 0 1.3 0.881 Comparative Comparative 1.2 44.1 01.2 0.902 Example 5B Example 1^(c) ^(a)I₂ value, ^(b)I_(21.6) value,^(c)120° C. polymerization

As shown in Table 4, the catalyst of the present invention hadrelatively enhanced reactivity for the olefin monomer having largesteric hindrance such as 1-butene since the molecular weight of thecopolymer of Example 23 (23A-23H) was higher than that of ComparativeExample 5 (5A-5B) and the density of the copolymer was lower than thatof Comparative Example 5 (5A-5B) when 1-butene was applied.Particularly, the catalyst compounds obtained in Examples 7, 15, and 17had a similar or higher polymerization activity compared to catalystcompounds obtained in Comparative Example 1, and even at 120° C. , thecatalyst compounds obtained in Example 2 showed a higher polymerizationactivity, a higher molecular weight, and a lower copolymer densitycompared to catalyst compounds obtained in Comparative Example 1.Therefore, the catalyst according to the present invention showedexcellent polymerization reactivity.

Accordingly, the transition metal complex and the catalyst compositionof the present invention including the transition metal complex hadimproved copolymerization reactivity in α-olefin polymerization comparedto a conventional catalyst composition. Therefore, when the catalystcomposition of the present invention was used in α-olefincopolymerization, a copolymer having lower density can be obtained.Therefore, when the catalyst composition of the present invention isused, a copolymer with a higher amount of α-olefin than the conventionalcatalyst composition can be obtained.

A transition metal complex of the present invention has a pentagon ringstructure having an amido group connected by a phenylene bridge in whicha stable bond is formed in the vicinity of the metal site, and thus, asterically hindered monomer can easily approach the transition metalcomplex. By using a catalyst composition including the transition metalcomplex according to the present invention, a linear low densitypolyolefin copolymer having a high molecular weight and a very lowdensity polyolefin copolymer having a density of 0.910 g/cc or less canbe produced in a polymerization of monomers having large sterichindrance. Further, the reactivity for the olefin monomer having largesteric hindrance is excellent.

While the present invention has been particularly shown and describedwith reference to exemplary embodiments thereof, it will be understoodby those of ordinary skill in the art that various changes in form anddetails may be made therein without departing from the spirit and scopeof the present invention as defined by the following claims.

1. A catalyst composition comprising: a transition metal complexrepresented by Formula 1 below; and at least one cocatalyst compoundselected from the group consisting of compounds represented by Formulae5, 6, and 7 below:

where, CY1 is a portion of a substituted or unsubstituted aliphatic oraromatic ring, M is a Group 4 transition metal; R₁s and R₂s are eachindependently one selected from the group consisting of: a hydrogenatom, a C₁₋₂₀ alkyl radical, a C₆₋₂₀ aryl radical, a silyl radical, aC₂₋₂₀ alkenyl radical, a C₇₋₂₀ alkylaryl radical, a C₇₋₂₀ arylalkylradical, and a metalloid radical of Group 14 substituted with a C₁₋₂₀hydrocarbyl, wherein R₁ and R₂ can be connected to each other by analkylidene radical containing a C₁₋₂₀ alkyl or aryl radical to form aring; each of the R₃s are independently one selected from the groupconsisting of: a hydrogen atom, a halogen radical, a C₁₋₂₀ alkylradical, a C₆₋₂₀ aryl radical, a C₁₋₂₀ alkoxy radical, a C₆₋₂₀ aryloxyradical, and an amido radical, wherein at least two R₃s can be connectedto each other to form an aliphatic or aromatic ring; and Q₁ and Q₂ areeach independently one selected from the group consisting of: a halogenradical, a C₁₋₂₀ alkylamido radical, a C₆₋₂₀ arylamido radical, a C₁₋₂₀alkyl radical, a C₂₋₂₀ alkenyl radical, a C₆₋₂₀ aryl radical, a C₇₋₂₀alkylaryl radical, a C₇₋₂₀ arylalkyl radical, and a C₁₋₂₀ alkylideneradical;—[Al(R₆)—O]_(a)—  Formula 5 where, each of the R₈s are independently oneselected from the group consisting of: a halogen radical; a C₁₋₂₀hydrocarbyl radical; and a C₁₋₂₀ hydrocarbyl radical substituted with ahalogen atom; and a is an integer of 2 or greater;D(R₈)₃   Formula 6 where, D is aluminum or boron, and R₈ is as describedabove; and[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  Formula 7 where, L is a neutral orcationic Lewis acid; H is a hydrogen atom; Z is a Group 13 atom; andeach of the As are independently a C₆₋₂₀ aryl or C₁₋₂₀ alkyl radical inwhich at least one hydrogen atom is substituted with a halogen atom, ora C₁₋₂₀ hydrocarbyl radical, C₁₋₂₀ alkoxy radical, or a phenoxy radical.2. The catalyst composition of claim 1, wherein the transition metalcomplex represented by Formula 1 is selected from the group consistingof compounds represented by the following Formulae:

where, each of the R₂s are independently a hydrogen atom or a methylradical, and Q₅ and Q₆ are each independently one selected from thegroup consisting of: a methyl, dimethylamido and chloride radical.
 3. Amethod of preparing a catalyst composition according to claim 1,comprising: bringing the transition metal complex represented by Formula1 below into contact with a compound represented by Formula 5 or 6 belowto obtain a mixture; and adding a compound represented by Formula 7below to the mixture:

where, CY1 is a portion of a substituted or unsubstituted aliphatic oraromatic ring, M is a Group 4 transition metal; R₁s and R₂s are eachindependently one selected from the group consisting of: a hydrogenatom, a C₁₋₂₀ alkyl radical, a C₆₋₂₀ aryl radical, a silyl radical, aC₂₋₂₀ alkenyl radical, a C₇₋₂₀ alkylaryl radical, a C₇₋₂₀ arylalkylradical, and a metalloid radical of Group 14 substituted with a C₁₋₂₀hydrocarbyl, wherein R₁ and R₂ can be connected to each other by analkylidene radical containing a C₁₋₂₀ alkyl or aryl radical to form aring; each of the R₃s are independently one selected from the groupconsisting of: a hydrogen atom, a halogen radical, a C₁₋₂₀ alkylradical, a C₆₋₂₀ aryl radical, a C₁₋₂₀ alkoxy radical, a C₆₋₂₀ aryloxyradical, and an amido radical, wherein at least two R₃s can be connectedto each other to form an aliphatic or aromatic ring; Q₁ and Q₂ are eachindependently one selected from the group consisting of: a halogenradical, a C₁₋₂₀ alkylamido radical, a C₆₋₂₀ arylamido radical, a C₁₋₂₀alkyl radical, a C₂₋₂₀ alkenyl radical, a C₆₋₂₀ aryl radical, a C₇₋₂₀alkylaryl radical, a C₇₋₂₀ arylalkyl radical; and a C₁₋₂₀ alkylideneradical; a is an integer of 2 or greater; each of the R₈s areindependently one selected from the group consisting of: a halogenradical, a C₁₋₂₀ hydrocarbyl radical, and a C₁₋₂₀ hydrocarbyl radicalsubstituted with a halogen atom; D is aluminum or boron; L is a neutralor cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 atom; andeach of the As are independently a C₆₋₂₀ aryl or C₁₋₂₀ alkyl radical inwhich at least one hydrogen atom is substituted with a halogen atom, ora C₁₋₂₀ hydrocarbyl radical, C₁₋₂₀ alkoxy radical, or a phenoxy radical.4. The method of claim 3, wherein the transition metal complexrepresented by Formula 1 is selected from the group consisting ofcompounds represented by the following Formulae:

where, each of the R₇s are independently a hydrogen atom or a methylradical, and Q₅ and Q₆ are each independently one selected from thegroup consisting of: a methyl, a dimethylamido and a chloride radical.5. The method of claim 3, wherein the molar ratio of the transitionmetal complex to the compound represented by Formula 5 or 6 is in therange of 1:2 to 1:5000, and the molar ratio of the transition metalcomplex to the compound represented by Formula 7 is in the range of 1:1to 1:25.
 6. A method of synthesizing an olefin polymer, wherein thecatalyst composition according to claim 1 is brought into contact with amonomer.
 7. The method of claim 6, wherein the monomer is at least oneselected from the group consisting of ethylene, propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-undecene 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.